Electroluminescent devices for lighting applications

0001This application claims priority to U.S. provisional application No. 61/296,680, filed Jan. 20, 2010, the disclosure of which is herein expressly incorporated by reference in its entirety.

0002The claimed invention was made by, on behalf of, and/or in connection with one or more of the following parties to a joint university corporation research agreement: Regents of the University of Michigan, Princeton University, The University of Southern California, and the Universal Display Corporation. The agreement was in effect on and before the date the claimed invention was made, and the claimed invention was made as a result of activities undertaken within the scope of the agreement.

FIELD OF THE INVENTION

0003The present invention relates to organic light emitting devices, and more particularly to organic light emitting devices that include a solution deposited emissive layer.

0004Organic light emitting devices (OLEDs) make use of thin organic films that emit light when voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination, and backlighting. Several OLED materials and configurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.

0005The color of an OLED device may be measured using CIE coordinates, which are well known to the art. Unless otherwise specified, CIE coordinates as used herein refer to 1931 CIE coordinates.

0006As used herein, the term “organic” includes polymeric materials as well as small molecule organic materials that may be used to fabricate organic opto-electronic devices. “Small molecule” refers to any organic material that is not a polymer, and “small molecules” may actually be quite large. Small molecules may include repeat units in some circumstances. For example, using a long chain alkyl group as a substituent does not remove a molecule from the “small molecule” class. Small molecules may also be incorporated into polymers, for example as a pendent group on a polymer backbone or as a part of the backbone. Small molecules may also serve as the core moiety of a dendrimer, which consists of a series of chemical shells built on the core moiety. The core moiety of a dendrimer may be a fluorescent or phosphorescent small molecule emitter. A dendrimer may be a “small molecule,” and it is believed that all dendrimers currently used in the field of OLEDs are small molecules.

0007As used herein, “top” means furthest away from the substrate, while “bottom” means closest to the substrate. Where a first layer is described as “disposed over” a second layer, the first layer is disposed further away from substrate. There may be other layers between the first and second layer, unless it is specified that the first layer is “in contact with” the second layer. For example, a cathode may be described as “disposed over” an anode, even though there are various organic layers in between.

0008As used herein, “solution processable” means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form. A “solution processed” layer refers to a layer that was deposited using a liquid medium. Examples of solution deposition techniques include spin coating, dip coating, slot dye coating, roll-to-roll coating and ink-jet printing.

0009More details on OLEDs, and the definitions described above, can be found in U.S. Pat. No. 7,279,704, which is incorporated herein by reference in its entirety.

SUMMARY OF THE INVENTION

0010An method of fabricating an organic light emitting device is provided. A first electrode is provided, over which the rest of the device will be fabricated. A first organic layer is deposited over the first electrode via solution processing. The first organic layer includes: <ul id="ul0003" list-style="none"><li id="ul0003-0001" num="0000"><ul id="ul0004" list-style="none"><li id="ul0004-0001" num="0011">i. an organic host material of the first organic layer;</li><li id="ul0004-0002" num="0012">ii. a first organic emitting material of the first organic layer;</li><li id="ul0004-0003" num="0013">iii. a second organic emitting material of the first organic layer; <br /> A second organic layer is deposited over and in direct contact with the first organic layer. The second organic layer includes an organic emitting material of the second organic layer. A second electrode is then deposited over the second organic layer. The device may include other layers. </li></ul></li></ul>

0014Preferably, the first organic emitting material of the first organic layer has a peak emissive wavelength in the visible spectrum of 590-700 nm, the second organic emitting material of the first organic layer has a peak emissive wavelength in the visible spectrum at 500-590 nm and the organic emitting material of the second organic layer has a peak emissive wavelength in the visible spectrum of 400-500 nm.

0015Preferably, the first organic emitting material of the first organic layer is present in the first organic layer in a concentration of 0.01-5 wt %, and the second organic emitting material of the first organic layer is present in the first organic layer in a concentration that is 1.1 to 500 times the concentration of the concentration of the first organic emitting material. In addition, the second organic emitting material of the first organic layer is present in an amount not more than 40 wt %. Percentages are given as weight percentages of the organic layer after fabrication, and may generally be determined by using the relative weight percentages in solution of the various materials to be deposited, because the solvent evaporates.

0016More preferably, the first organic emitting material of the first organic layer is present in the in the first organic layer in a concentration of 0.2-4 wt %, and the second organic emitting material of the first organic layer is present in the first organic layer in a concentration that is 2 to 200 times the concentration of the concentration of the first organic emitting material. In addition, the second organic emitting material of the first organic layer is present in an amount not more than 40 wt %.

0017Preferably, the first organic emitting material of the first organic layer, the second organic emitting material of the first organic layer, and the organic emitting material of the second organic layer are all small molecule materials.

0018Preferably, the second organic layer comprises an organic host and the organic emitting material of the second organic layer. Preferably, the second organic layer is deposited by vapor deposition, where the organic host of the second organic layer and the organic emitting material of the second organic layer are co-deposited. Vapor deposition includes vapor thermal evaporation (VTE), organic vapor phase deposition (OVPD), and organic vapor jet printing (OVJP).

0019Preferably, the method also includes, prior to depositing the first organic layer, the steps of: <ul id="ul0005" list-style="none"><li id="ul0005-0001" num="0000"><ul id="ul0006" list-style="none"><li id="ul0006-0001" num="0020">depositing a third organic layer comprising an organic material of the third organic layer over the first electrode via solution processing; and</li><li id="ul0006-0002" num="0021">depositing a fourth organic layer comprising an organic material of the fourth organic layer over the third organic layer via solution processing. <br /> Preferably the third organic layer does not dissolve when the fourth organic layer is deposited, and the fourth organic layer does not dissolve when the first organic layer is deposited. </li></ul></li></ul>

0022Preferably, the organic light emitting device emits light having a CIE coordinate of x coordinate in the range of 0.15-0.65, and y coordinate in the range of 0.1-0.7. More preferably, the organic light emitting device emits light having a CIE coordinate of x coordinate in the range of 0.25-0.5, and y coordinate in the range of 0.2-0.5.

0023The layers may include materials other than those specified. For example, the first organic layer may further comprises a third organic emitting material of the first organic layer.

BRIEF DESCRIPTION OF THE DRAWINGS

0024<figref idref="DRAWINGS">FIG. 1</figref> shows an organic light emitting device.

0025<figref idref="DRAWINGS">FIG. 2</figref> shows an inverted organic light emitting device that does not have a separate electron transport layer.

0026<figref idref="DRAWINGS">FIG. 3</figref> shows an organic light emitting device including a solution deposited emissive layer that includes co-doped emissive materials.

0027<figref idref="DRAWINGS">FIG. 4</figref> shows an organic light emitting device including a solution deposited emissive layer that includes co-doped emissive materials, with more detail than <figref idref="DRAWINGS">FIG. 3</figref>.

0028<figref idref="DRAWINGS">FIG. 5</figref> shows an organic light emitting device including a vapor deposited emissive layer that includes co-doped emissive materials.

0029<figref idref="DRAWINGS">FIG. 6</figref> shows a 1931 CIE diagram illustrating a CIE coordinate for a white device having a solution deposited co-doped emissive layer.

0030<figref idref="DRAWINGS">FIG. 7</figref> shows an emissive spectrum for the white device that generated the CIE coordinate of <figref idref="DRAWINGS">FIG. 6</figref>.

0031<figref idref="DRAWINGS">FIG. 8</figref> shows a 1931 CIE diagram illustrating the variance in the CIE coordinates of devices fabricated using a vapor deposition technique.

0032<figref idref="DRAWINGS">FIG. 9</figref> shows a magnified portion of the 1931 CIE diagram of <figref idref="DRAWINGS">FIG. 8</figref>.

0033<figref idref="DRAWINGS">FIG. 10</figref> shows spectra for the devices fabricated using a vapor deposition technique.

DETAILED DESCRIPTION

0034Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an “exciton,” which is a localized electron-hole pair having an excited energy state, is formed. Light is emitted when the exciton relaxes via a photoemissive mechanism. In some cases, the exciton may be localized on an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.

0035The initial OLEDs used emissive molecules that emitted light from their singlet states (“fluorescence”) as disclosed, for example, in U.S. Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescent emission generally occurs in a time frame of less than 10 nanoseconds.

0036More recently, OLEDs having emissive materials that emit light from triplet states (“phosphorescence”) have been demonstrated. Baldo et al., “Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices,” Nature, vol. 395, 151-154, 1998; (“Baldo-I”) and Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence,” Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) (“Baldo-II”), which are incorporated by reference in their entireties. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporated by reference.

0037<figref idref="DRAWINGS">FIG. 1</figref> shows an organic light emitting device <b>100</b>. The figures are not necessarily drawn to scale. Device <b>100</b> may include a substrate <b>110</b>, an anode <b>115</b>, a hole injection layer <b>120</b>, a hole transport layer <b>125</b>, an electron blocking layer <b>130</b>, an emissive layer <b>135</b>, a hole blocking layer <b>140</b>, an electron transport layer <b>145</b>, an electron injection layer <b>150</b>, a protective layer <b>155</b>, and a cathode <b>160</b>. Cathode <b>160</b> is a compound cathode having a first conductive layer <b>162</b> and a second conductive layer <b>164</b>. Device <b>100</b> may be fabricated by depositing the layers described, in order. The properties and functions of these various layers, as well as example materials, are described in more detail in U.S. Pat. No. 7,279,704 at cols. 6-10, which are incorporated by reference.

0038More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F.sub.4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, disclose examples of cathodes including compound cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The theory and use of blocking layers is described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers may be found in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.

0039<figref idref="DRAWINGS">FIG. 2</figref> shows an inverted OLED <b>200</b>. The device includes a substrate <b>210</b>, a cathode <b>215</b>, an emissive layer <b>220</b>, a hole transport layer <b>225</b>, and an anode <b>230</b>. Device <b>200</b> may be fabricated by depositing the layers described, in order. Because the most common OLED configuration has a cathode disposed over the anode, and device <b>200</b> has cathode <b>215</b> disposed under anode <b>230</b>, device <b>200</b> may be referred to as an “inverted” OLED. Materials similar to those described with respect to device <b>100</b> may be used in the corresponding layers of device <b>200</b>. <figref idref="DRAWINGS">FIG. 2</figref> provides one example of how some layers may be omitted from the structure of device <b>100</b>.

0040The simple layered structure illustrated in <figref idref="DRAWINGS">FIGS. 1 and 2</figref> is provided by way of non-limiting example, and it is understood that embodiments of the invention may be used in connection with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. Functional OLEDs may be achieved by combining the various layers described in different ways, or layers may be omitted entirely, based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many of the examples provided herein describe various layers as comprising a single material, it is understood that combinations of materials, such as a mixture of host and dopant, or more generally a mixture, may be used. Also, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device <b>200</b>, hole transport layer <b>225</b> transports holes and injects holes into emissive layer <b>220</b>, and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an “organic layer” disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise multiple layers of different organic materials as described, for example, with respect to <figref idref="DRAWINGS">FIGS. 1 and 2</figref>.

0041Structures and materials not specifically described may also be used, such as OLEDs comprised of polymeric materials (PLEDs) such as disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. By way of further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example as described in U.S. Pat. No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in <figref idref="DRAWINGS">FIGS. 1 and 2</figref>. For example, the substrate may include an angled reflective surface to improve out-coupling, such as a mesa structure as described in U.S. Pat. No. 6,091,195 to Forrest et al., and/or a pit structure as described in U.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entireties.

0042Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For the organic layers, preferred methods include thermal evaporation, ink-jet, such as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties, organic vapor phase deposition (OVPD), such as described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (OVJP), such as described in U.S. patent application Ser. No. 10/233,470, which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere. For the other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink jet and OVJD. Other methods may also be used. The materials to be deposited may be modified to make them compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons is a preferred range. Materials with asymmetric structures may have better solution processability than those having symmetric structures, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.

0043Devices fabricated in accordance with embodiments of the invention may be incorporated into a wide variety of consumer products, including flat panel displays, computer monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads up displays, fully transparent displays, flexible displays, laser printers, telephones, cell phones, personal digital assistants (PDAs), laptop computers, digital cameras, camcorders, viewfinders, micro-displays, vehicles, a large area wall, theater or stadium screen, or a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present invention, including passive matrix and active matrix. Many of the devices are intended for use in a temperature range comfortable to humans, such as 18 degrees C. to 30 degrees C., and more preferably at room temperature (20-25 degrees C.).

0044The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices, such as organic transistors, may employ the materials and structures.

0045An method of fabricating an organic light emitting device is provided. A first electrode is provided, over which the rest of the device will be fabricated. A first organic layer is deposited over the first electrode via solution processing. The first organic layer includes: <ul id="ul0007" list-style="none"><li id="ul0007-0001" num="0000"><ul id="ul0008" list-style="none"><li id="ul0008-0001" num="0046">i. an organic host material of the first organic layer;</li><li id="ul0008-0002" num="0047">ii. a first organic emitting material of the first organic layer;</li><li id="ul0008-0003" num="0048">iii. a second organic emitting material of the first organic layer. <br /> A second organic layer is deposited over and in direct contact with the first organic layer. The second organic layer includes an organic emitting material of the second organic layer. A second electrode is then deposited over the second organic layer. The device may include other layers. </li></ul></li></ul>

0049<figref idref="DRAWINGS">FIG. 3</figref> shows an example of device <b>300</b> fabricated using the described method. The device is fabricated on a substrate <b>310</b>. The device includes a first electrode <b>320</b>, emitting layers <b>330</b> disposed over the first electrode <b>320</b>, and a second electrode <b>340</b> disposed over the emitting layers <b>330</b>. Emitting layers <b>330</b> include first organic layer <b>332</b> and second organic layer <b>334</b>. First electrode <b>320</b> is preferably an anode and second electrode <b>340</b> is preferably a cathode, but other configurations may be used.

0050First electrode <b>320</b> may be provided by any suitable method, including the purchase of commercially available substrates pre-coated with indium tin oxide (ITO) or other electrode material. First organic layer <b>332</b> is deposited via solution deposition over first electrode <b>320</b>. The solution used to deposit first organic layer <b>332</b> includes a solvent, the organic host material of the first organic layer; the first organic emitting material of the first organic layer; and the second organic emitting material of the first organic layer. Other materials may be included. Second organic layer <b>334</b> is deposited over and in direct contact with first organic layer <b>332</b>. Second organic layer <b>334</b> includes an organic emitting material of the second organic layer. Second electrode <b>340</b> is subsequently deposited over second organic layer <b>334</b> by any suitable technique.

0051Device <b>300</b> as illustrated also includes optional layers. A third organic layer <b>350</b> and a fourth organic layer <b>360</b> are disposed between emitting layers <b>330</b> and first electrode <b>320</b>. Where first electrode <b>320</b> is an anode, third organic layer <b>350</b> may be a hole injection layer and fourth organic layer may be a hole transport layer. A fifth organic layer <b>370</b> is disposed between emitting layers <b>330</b> and second electrode <b>340</b>. Where second electrode <b>340</b> is a cathode, fourth organic layer <b>370</b> may include a hole blocking layer, and an electron transport layer. Third, fourth and fifth organic layers <b>350</b>, <b>360</b> and <b>370</b> may include sublayers, and may include other layers useful in various OLED architectures, many of which are described with respect to <figref idref="DRAWINGS">FIGS. 1 and 2</figref>.

0052Preferably, the first organic emitting material of first organic layer <b>332</b> has a peak emissive wavelength in the visible spectrum of 590-700 nm, the second organic emitting material of first organic layer <b>332</b> has a peak emissive wavelength in the visible spectrum at 500-590 nm and the organic emitting material of second organic layer <b>334</b> has a peak emissive wavelength in the visible spectrum of 400-500 nm. These peak wavelengths correspond roughly to red, green, and blue emitters, and are useful for obtaining a device that emits white light that would be useful, for example, for general illumination purposes.

0053Preferably, the first organic emitting material of first organic layer <b>332</b> is present in first organic layer <b>332</b> in a concentration of 0.01-5 wt %, and the second organic emitting material of first organic layer <b>332</b> is present in the first organic layer in a concentration that is 1.1 to 500 times the concentration of the concentration of the first organic emitting material. In addition, the second organic emitting material of first organic layer <b>332</b> is present in an amount not more than 40 wt %. Percentages are given as weight percentages of the organic layer after fabrication, and may generally be determined by using the relative weight percentages in solution of the various materials to be deposited, because the solvent evaporates. More preferably, the first organic emitting material of first organic layer <b>332</b> is present in the in first organic layer <b>332</b> in a concentration of 0.2-4 wt %, and the second organic emitting material of first organic layer <b>332</b> is present in first organic layer <b>332</b> in a concentration that is 2 to 200 times the concentration of the concentration of the first organic emitting material. In addition, the second organic emitting material of first organic layer <b>332</b> is preferably present in an amount not more than 40 wt %.

0054Preferably, the first organic emitting material of first organic layer <b>332</b>, the second organic emitting material of first organic layer <b>332</b>, and the organic emitting material of second organic layer <b>334</b> are all small molecule materials. Many small molecule materials are suitable for solution deposition, or may be readily modified to render them suitable for solution deposition using known techniques involving the addition of bulky substituents.

0055Preferably, second organic layer <b>334</b> comprises an organic host and the organic emitting material of second organic layer <b>334</b>. Preferably, second organic <b>334</b> layer is deposited by vapor deposition, where the organic host of second organic layer <b>334</b> and the organic emitting material of second organic layer <b>334</b> are co-deposited. Vapor deposition includes vapor thermal evaporation (VTE), organic vapor phase deposition (OVPD), and organic vapor jet printing (OVJP). Vapor deposition is preferred because treatments to render underlying layers (such as first organic layer <b>332</b>) insolvent often involve steps that would be detrimental to emitting materials. However, where techniques exist for solution depositing one emissive layer over another, those techniques may be used to deposit second organic layer <b>334</b> over first organic layer <b>332</b>.

0056Third and fourth organic layers <b>350</b> and <b>360</b>, when present, are preferably deposited via solution deposition techniques. Because these organic layers do not include emitting materials, material and processing choices are readily available that render these layers insoluble in a solvent used to deposit subsequent layers. One such process choice is baking to cross-link the material, rendering it insoluble.

0057Preferably, the organic light emitting device emits light having a CIE coordinate of x coordinate in the range of 0.15-0.65, and y coordinate in the range of 0.1-0.7. More preferably, the organic light emitting device emits light having a CIE coordinate of x coordinate in the range of 0.25-0.5, and y coordinate in the range of 0.2-0.5. These CIE coordinates are readily obtainable using the preferred peak wavelength choices for the emitting materials of the device.

0058One issue that the inventors have identified and solved relates to the first organic layer. The preferred percentages are useful for fabricating a device that emits white light. However, using the preferred wavelengths and amounts for the first and second emitting materials of first organic layer <b>332</b> means that first organic layer <b>332</b> includes a small amount of red dopant, and a larger amount of green dopant. To achieve white emission from the overall device, the amount of red dopant will generally be small, both in absolute terms and relative to the amount of green dopant. This is because when a red dopant is co-doped with a green dopant, excitons may preferentially move to the red dopant or transfer from the green dopant to the red dopant due to the lower energy of the red dopant. Due to this preferential emission from the red dopant, a significantly smaller amount of red and larger amount of green is needed than if the materials were in separate layers. In addition, the amount of emission from red dopant relative to green dopant is highly sensitive to small variations in the concentrations of the dopants, again due to the preferential emission from the red dopant.

0059Controlling the amount of dopant deposited via vapor deposition techniques such as VTE generally involves adjusting temperatures, aperture sizes and relative flow rates of materials. The variance in the amount of dopant deposited from run to run is typically about 5%. So if it were desired to deposit a layer having 1 wt % of red dopant, the actual amount of red dopant would be about 0.95 wt % to 1.05 wt %. Where the device includes a layer having co-doped red and green dopants (and the green dopant will also be expected to have a 5% variance), the variance is large enough to significantly alter the CIE coordinates of a device.

0060However, controlling the amount of dopant for solution process techniques generally involves weighing the various materials and adding them to a solvent in carefully controlled amounts. In the inventors laboratory, a weight as low as 0.001 g of red dopant can be measured for use in solution using a micro balance with a precision of 0.00001 g (plus or minus). In this case, variance is 1%. This reduction in variance is expected to significantly improve the reproducibility of the CIE coordinates of the finished device.

0061Particularly preferred concentrations for a layer including only red and green dopants are about 1 wt % for the red dopant and about 12 wt % for the green dopant. Other combinations of dopants, and other concentrations may be used. A solution processed emitting layer may include three or more emitting materials. An example of this useful for a white-emitting device is a layer that includes 72 wt % host, 20 wt % green emitter, 5 wt % yellow and 3 wt % red. Another example is 68.9 wt % host, 30 wt % green, 1% red<b>1</b>, and 0.1% red<b>2</b> where red<b>1</b> and red<b>2</b> are different red emitting materials.

0062Other types of dopants may be used, and dopants in addition to those specifically described may be used. For example, the first organic layer may further comprises a third organic emitting material of the first organic layer. A third organic dopant may be useful, for example, to add an additional emission color to fine tune the overall emission of the device, to adjust conductivity, or other uses.

0063Emissive “dopants” may include phosphorescent emitting organic materials or fluorescent organic emitting materials.

0064A preferred device structure is illustrated in <figref idref="DRAWINGS">FIG. 4</figref>. Device <b>400</b> is a preferred specific structure of device <b>300</b>. Device <b>400</b> is fabricated on a substrate <b>410</b>, and includes, in order, anode <b>420</b>, solution processed organic hole injection layer <b>452</b>, solution processed organic hole transport layer <b>454</b>, solution processed organic emissive layer <b>432</b>, VTE deposited organic emissive layer <b>434</b>, VTE deposited organic blocking layer <b>462</b>, VTE deposited organic electron transport layer <b>464</b> and cathode <b>440</b>. Solution processed organic emissive layer <b>432</b> includes a host and red and green emitting dopants, and VTE deposited organic emissive layer <b>434</b> includes a host and a blue emitting dopant.

0065<figref idref="DRAWINGS">FIG. 5</figref> shows a comparative example that does not include a solution deposited layer having multiple emissive dopants. Device <b>500</b> is fabricated on a substrate <b>510</b>, and includes, in order, anode <b>520</b>, VTE deposited organic hole injection layer <b>552</b>, VTE deposited organic hole transport layer <b>554</b>, VTE deposited organic emissive layer <b>532</b>, VTE deposited organic emissive layer <b>534</b>, VTE deposited organic blocking layer <b>562</b>, VTE deposited organic electron transport layer <b>464</b> and cathode <b>440</b>. VTE deposited organic emissive layer <b>532</b> includes a host and red and green emitting dopants, and VTE deposited organic emissive layer <b>534</b> includes a host and a blue emitting dopant.

0066<figref idref="DRAWINGS">FIG. 6</figref> shows a CIE diagram. The star is located at a target CIE coordinate that is desirable for white emission. The curve on which the star is located is the well-known black-body radiation curve, which describes the color of thermal radiation from an object that absorbs all electromagnetic radiation that falls on it (a “black body”). <figref idref="DRAWINGS">FIG. 7</figref> shows a target spectrum calculated using the emission spectra of the red, green and blue emitting materials of Example 1.

0000Materials

0067The following materials were used in the Examples:

0068<chemistry id="CHEM-US-00001" num="00001"><img file="US8288187B2_D0001.tif" /></chemistry><chemistry id="CHEM-US-00002" num="00002"><img file="US8288187B2_D0002.tif" /></chemistry><chemistry id="CHEM-US-00003" num="00003"><img file="US8288187B2_D0003.tif" /></chemistry><br /> LG101 and LG201, available for purchase from LG Chemical Corporation of Seoul, Korea. NS60, available for purchase from Nippon Steel Chemical Company of Tokyo, Japan.

EXAMPLES

Example 1

All VTE White Device (Comparative Example)

0069As a comparative example, white OLEDs were fabricated using standard vacuum thermal evaporation (VIE) techniques to fabricate the entire device. These devices had the structure shown in <figref idref="DRAWINGS">FIG. 5</figref>. The materials and thicknesses of the layers were as follows:

0000ITO (80 nm)/LG101 (10 nm)/NPD (45 nm)/NS-60:Green Dopant:Red Dopant-1 (69:30:1; 20 nm)/Host-2:Blue Dopant-1: (80:20; 7.5 nm)/Host-2 (5 nm)/LG201 (45 nm)/LiF/Al

0070Seven VTE white devices were fabricated in different batches. The emission of these devices was measured, and the CIE coordinates of the devices are plotted in <figref idref="DRAWINGS">FIGS. 8 and 9</figref>. All seven devices were carefully made to have the same in structure, composition, and thickness. However, the colors are quite different by different batches. The average CIE coordinate of 7 batches is (0.424±0.007, 0.413±0.014).

0071The color difference between different devices can be described by MacAdam Ellipses, which are a well-known measure of human ability to differentiate color. A MacAdam Ellipse is a region on a CIE diagram inside of which a particular number of humans can not differentiate between colors. At a distance of one “step,” from a target CIE coordinate, 68% of people can perceive a color difference. 68% is the percentage that falls within one standard deviation on a bell curve. At a distance of two steps, 95% of people can perceive a color difference, where 95% is the percentage that falls within two standard deviations on a bell curve, and so on. The lighting industry generally desires that the color of a light used for illumination be reproducible within a 3- or 4-step MacAdam ellipse. If color reproducibility is too low, a viewer looking at two sources of illumination would perceive significant differences. For example, the different panels of a ceiling light might appear to have different colors, or there might be a significantly perceivable variation within a panel, which is undesirable.

0072<figref idref="DRAWINGS">FIG. 8</figref> shows the CIE coordinates of the seven devices having the structure shown in <figref idref="DRAWINGS">FIG. 5</figref>. <figref idref="DRAWINGS">FIG. 9</figref> shows the same data as <figref idref="DRAWINGS">FIG. 8</figref>, but the relevant region of the diagram is magnified. <figref idref="DRAWINGS">FIG. 10</figref> shows the measured spectra for the seven devices. It can be seen that there is a significant spread in the CIE coordinates of the different devices, and that they are all well outside of a 3-step MacAdam ellipse centered around the average of the CIE coordinates (0.424, 0.413) of the seven devices. The 7-step MacAdam ellipse can barely enclose the 7 device colors, which is out of industrial standard tolerance specification. This means that color reproducibility is not reliable for the VTE devices notwithstanding the care taken to achieve color reproducibility. The inventors attribute this variation in color to the sensitivity of the co-doped green and red emitting layer to the percentage of red dopant, and the relatively high variation in this percentage that occurs with a VTE deposition process.

Example 2

Hybrid White Device

0073A device was fabricated having the structure shown in <figref idref="DRAWINGS">FIG. 4</figref>. The hole injecting material HIL-1 (as the host material) along with Conducting dopant-1 were dissolved in a cyclohexanone solution. The amount of Conducting dopant-1 in the solution was 10 wt % relative to the host material HIL-1. The total concentration of the HIL-1 and Conducting dopant-1 was 0.5 wt % in cyclohexanone. To form the hole injection layer (HIL), the solution was spin-coated at 4000 rpm for 60 seconds onto a patterned indium tin oxide (ITO) electrode. The resulting film was baked for 30 minutes at 250° C. The film became insoluble after baking.

0074On top of the HIL, a hole transporting layer (HTL) and then emitting layer (EML) were also formed by spin-coating. The HTL was made by spin-coating a 1 wt % solution of the hole transporting material HTL-1 in toluene at 4000 rpm for 60 seconds. The HTL film was baked at 200° C. for 30 minutes. After baking, the HTL became an insoluble film.

0075The red and green EML was composed of a host material (Host-1) and a red and a green phosphorescent dopant (Red dopant-1 and Green dopant-1) as the emitting material. To form the EML, a toluene solution containing Host-1, Green dopant-1, and Red dopant (of total 0.75 wt %) with a Host-1:Green dopant-1:Red dopant-1 weight ratio of 87:12:1, was spin-coated onto the insoluble HTL at 1000 rpm for 60 seconds, and then baked at 100° C. for 60 minutes.

0076The blue EML was deposited using thermal evaporation. The 10 nm of blue host (Host-2) and Blue dopant-1 was co-evaporated with ratio of 90:10. On top of blue EML, 5 nm neat Host-2 was evaporated to build blocking layer (BL). The electron transport layer (containing Alq3), the electron injection layer (containing LiF), and the aluminum electrode were sequentially vacuum deposited.

0077When finished, the device of Example 2 had the structure:

0000ITO (120 nm)/HIL-1:Conducting Dopant-1 (90:10; 5 nm)/HTL-1 (10 nm)/Host-1:Green Dopant-1:Red Dopant-1 (87:12:1; 25 nm)/Host-2:Blue Dopant-1: (90:10; 10 nm)/Host-2 (5 nm)/Alq₃(40 nm)/LiF/Al

0078The CIE coordinate and spectrum of the hybrid white device of Example 2 are shown in <figref idref="DRAWINGS">FIGS. 6 and 7</figref>, respectively. The device performance is described in TABLE 1. At 1000 cd/m2, the power efficiency was 11 lm/W with color rendering index (CRI) <b>78</b>, and correlated color temperature (CCT) corresponding to the white color was 2800K degree.

0079<tables id="TABLE-US-00001" num="00001"><table frame="none" colsep="0" rowsep="0"><tgroup align="left" colsep="0" rowsep="0" cols="1"><colspec colname="1" colwidth="217pt" align="center" /><thead><row><entry namest="1" nameend="1" rowsep="1">TABLE 1</entry></row><row><entry namest="1" nameend="1" align="center" rowsep="1" /></row><row><entry>Hybrid white device performances of Example 2</entry></row><row><entry namest="1" nameend="1" align="center" rowsep="1" /></row></thead><tbody valign="top"><row><entry /></row></tbody></tgroup><tgroup align="left" colsep="0" rowsep="0" cols="2"><colspec colname="1" colwidth="168pt" align="left" /><colspec colname="2" colwidth="49pt" align="char" char="." /><tbody valign="top"><row><entry>Power Efficiency (lm/W) @ 1,000 cd/m2</entry><entry>11</entry></row><row><entry>Correlated Color Temperature (CCT) (K) @ 1,000 cd/m2</entry><entry>2800</entry></row><row><entry>Color Rendering Index (CRI) @ 1,000 cd/m2</entry><entry>78</entry></row><row><entry>Color Coordinate, CIE(x, y) @ 1,000 cd/m2</entry><entry>(0.453, 0.411)</entry></row><row><entry>Lifetime LT80 (hours) @ 4,000 cd/m2</entry><entry>100</entry></row><row><entry>(A brightness decay to 80% of initial level 4,000 cd/m2</entry></row><row><entry namest="1" nameend="2" align="center" rowsep="1" /></row></tbody></tgroup></table></tables>

0080It is understood that the various embodiments described herein are by way of example only, and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without deviating from the spirit of the invention. The present invention as claimed may therefore includes variations from the particular examples and preferred embodiments described herein, as will be apparent to one of skill in the art. It is understood that various theories as to why the invention works are not intended to be limiting.